JPH0569143B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a chromium complex compound and a method for dyeing cellulose fibers or cellulosic fiber-containing fiber materials using the same. PRIOR ART Reactive dyes are used in large quantities for dyeing cellulose fibers because of their excellent fastness properties.
For example, a reactive dye having a reactive group such as dichlorotriazinyl, monochlorotriazinyl, fluorochloropyrimidinyl, dichloroquinoxazinyl, methylsulfonylpyrimidinyl, vinylsulfonyl, sulfatoethylsulfonyl, etc. is used as an acid binder. or substances that release acid binders by the action of heat (e.g., sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, sodium pyrophosphate, pyrophosphoric acid) Potassium, sodium bicarbonate, sodium trichloroacetate) can be used alone or in combination of two or more to create a dye bath.
Adjust the pH value to 10 or higher, and in the presence of neutral electrolytes such as sodium chloride and sodium sulfate,
Cellulose fibers are dyed at temperatures below 100°C. On the other hand, mixed fiber materials (blends) containing cellulose fibers are increasingly being used as textile materials for clothing, and among them, blends of polyester fiber and cotton (hereinafter referred to as T/C blends) are suitable for clothing and are economical. It came to be used in large quantities because of its superior properties. T/C blends are usually dyed using reactive dyes and disperse dyes in the following manner. (1) One-bath two-step method First, the polyester fiber side is dyed with a disperse dye using a carrier dyeing method, high temperature dyeing method, etc., and then the cotton side is dyed with a reactive dye in the same bath. Or stain in the reverse order. (2) Two-bath method First, the polyester fiber side is colored as described above, and then the cotton side is dyed in a separate bath, or in the reverse order. (3) One-bath, one-stage method The polyester fiber side and the cotton side are dyed in the same bath and in one dyeing operation. The following dye is described in JP-A-60-76565 as a brown reactive dye for cotton suitable for dyeing T/C blend in one step in one bath.

[C] Problems to be Solved by the Invention The above-mentioned dyes described as reactive dyes suitable for T/C mixed one-bath dyeing are inferior in color yield, cohesion, etc. The quality is somewhat insufficient as a reactive dye for one-stage dyeing. Means to solve the problem We are conducting intensive research to develop a brown reactive dye that is sufficiently suitable for the T/C mixed one-bath one-stage dyeing method and has improved the above-mentioned problems (color yield, cohesiveness). As a result of these efforts, we have arrived at the present invention. That is,
The present invention provides the formula (1) in the free acid form.

[In formula (1), X ₁ and X ₂ are each independently H, CH ₃ ,
OCH ₃ , NHCOCH ₃ or NHCONH ₂ , Y ₁ , Y ₂
are each independently

【formula】

[Formula] or -Cl, n represents 1 or 2, and K ⁺ represents a cationic group] A chromium complex compound and a method for dyeing cellulose fiber materials characterized by using the same provide. The chromium complex compound represented by formula (1) is
Not only is it suitable for dyeing by a one-bath one-step process carried out in the presence of an acid binder, but also especially in the formula (1).
Y ₁ and Y ₂ together

[Formula] or

In the case of [Formula], the T/C mixture can be uniformly dyed at a temperature of 95 to 150℃ in the presence of a disperse dye by simply adding a buffering agent that maintains the dye bath at pH 5 to 9. 1 bath 1
It has extremely advantageous properties for step dyeing. Of course, excellent effects can be obtained not only with T/C mixtures but also with fiber materials consisting only of cellulose fibers. The chromium complex compound represented by formula (1) is a T/C mixed compound.
Not only is it highly suitable for one-stage bath dyeing, but it also exhibits particularly good color yield and cohesion, as well as excellent build-up properties, solubility, and other properties. The chromium complex compound of the present invention can be applied to cotton, rayon,
Remarkable effects can be obtained when dyeing cellulose fibers such as linen and T/C blends, but other polyester fibers and rayon; cotton or rayon with triacetate fibers, polyacrylonitrile fibers, modified polyacrylonitrile fibers, polyamide fiber,
Disperse dyes are used for dyeing blended products with wool, silk, etc.
Excellent effects can be obtained even when dyeing is performed in combination with acidic metal-containing dyes, cationic dyes, etc. The chromium complex compound represented by formula (1) of the present invention is synthesized, for example, by the following method. That is, first, 1 mole of 2-aminobenzoic acid is diazotized to form 4-
Coupling was performed with 1 mole of hydroxy-7-aminonaphthalene-2-sulfonic acid in a weak alkaline state, and then 0.5 mole of chromium sulfate Cr ₂ (SO ₄ ) ₃ was added and reacted at 95-100°C under a weak acidity to form the formula (2).

A compound represented by the formula is obtained, and then 1 mole of the compound represented by the formula (2) and 2 moles of cyanuric chloride are mixed in water, for example.
The reaction is carried out at 10°C or lower to obtain a compound represented by the following formula (3).

[ka] Then equation (4)

[In formula (4), X ₁ and X ₂ each independently represent H, CH ₃ , OCH ₃ , NHCOCH ₃ or NHCONH ₂ , and n represents 1 or 2]

A compound of formula (5) is obtained by reacting 2 moles of the compound represented by formula (3) in water at a temperature of 40 to 70°C, for example. (Equivalent to the case where both Y ₁ and Y ₂ are Cl in formula (1))

[In the formula, X ₁ , X ₂ and n represent the same meanings as above] In formula (1), Y ₁ and/or Y ₂

【formula】 or

If [formula] is the case, then formula (5) For the compound represented by

【formula】

The compound represented by formula (1) is obtained by reacting 1 to 3 moles of the compound represented by formula (1) in water, for example, at a temperature of 80 to 100°C. The compound represented by formula (1) is usually separated as an alkali metal salt such as Na, K, Li, etc., but if desired, the reaction solution containing the alkali metal salt of formula (1) may be separated by ammonia, methylamine, It may be treated with ethylamine, propylamine, monoethanolamine, diethanolamine, triethanolamine, etc. and separated into their ammonium salts, alkylamine salts, alkanolamine salts, etc. Specific examples of compounds represented by formula (4) used in producing the chromium complex compound of formula (1) include:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 etc. These are the following formulas

[In the formula, n represents the same meaning as above]

The compound represented by the following formula

[Formula] [In the formula, X ₁ and X ₂ have the same meanings as above]
It can be obtained by coupling. Next, a method for dyeing cellulose fibers using the chromium complex compound represented by formula (1) of the present invention will be explained. When dyeing fiber materials consisting only of cellulose fibers by dip dyeing, a dye bath is prepared from the chromium complex compound of the present invention, inorganic salts (e.g., sodium sulfate, sodium chloride, etc.), the fibers are immersed,
After dyeing at ~90°C for 10 to 60 minutes, an acid binder is added if necessary, and dyeing is further carried out at the same temperature for 20 to 60 minutes. In this case, it is also possible to adopt a method in which the acid binder is added to the dye bath from the beginning and dyeing is carried out. In addition to the immersion dyeing method, dyeing can also be carried out by a batting dyeing method or a printing method according to conventional methods. In addition, in the above chromium complex compound of formula (1), Y ₁ and Y ₂ are both

[Formula] or

In the case of [Formula], a sufficiently good effect can usually be obtained without using a neutralizing agent or a buffering agent, but Y ₁
and/or when Y ₂ is chlorine, it is preferred to use a neutralizing agent or a buffering agent. For example, in the one-bath one-step dyeing of T/C mixture using the chromium complex compound and disperse dye of the present invention, in formula (1),
Y ₁ and/or Y ₂

[Formula] or

If [Formula] is the case, it is performed as follows. From the chromium complex compound of formula (1) of the present invention, a disperse dye, an inorganic salt if necessary, a buffer that maintains the pH value between 5 and 9, a surfactant (dispersant, penetrant), and a reduction inhibitor. A dye bath is prepared, the T/C mixture is immersed in this, and dyeing is carried out at 95 to 150°C for 20 to 90 minutes. In this case, by using a disperse dye that has sufficient resistance to alkali, dyeing can also be carried out by a method of dyeing in the presence of an ordinary acid binder. The chromium complex compound (1) of the present invention can also be used for blended products other than T/C blends, such as blended products of cellulose fibers and polyamide fibers (nylon, wool, silk, etc.), polyacrylic fibers, acid-modified polyester fibers, etc. It is dyed in the same manner as above using a combination of acidic dyes, basic dyes, etc. The compounds of the present invention can be used alone or in combination of two or more. In addition, when an acid binder is present, sodium carbonate, potassium carbonate, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, potassium pyrophosphate,
Sodium pyrophosphate, sodium bicarbonate, sodium trichloroacetate, etc. are used as buffering agents.
Sodium acetate, monosodium phosphate - diphosphoric acid
Sodium, maleic acid-borax, etc. are used. Examples The present invention will be explained in more detail by examples. In the examples, parts are by weight, and sulfonic acid groups in each formula are expressed in the form of free acid. Example 1

[Chemical] 3.8 parts of cyanuric chloride was added to a solution consisting of 20 parts of water, 30 parts of ice, and 0.5 part of a 10% Liponox NA (manufactured by Lion Oil Co., Ltd., dispersant) aqueous solution, and suspended for 30 minutes with stirring. Next, about 100 parts of an aqueous solution of a chromium complex compound obtained by treating 7.7 parts of 2-amino-6-(2'-carboxyphenylazo)-5-naphthol-7-sulfonic acid with chromium sulfate at 95°C under weak acidity. 30
The mixture was added dropwise for 1 minute while maintaining the temperature at 10° C. or below, and then reacted for 1 hour while maintaining the pH value at 7.0 to 7.5 with an aqueous sodium carbonate solution. Then 3-(2
-acetylamino-4-aminophenyl-azo)
- Add 9.2 parts of 1,5-naphthalenedisulfonic acid,
Heat to 50-55℃ and check PH value with sodium carbonate aqueous solution
Stirring was continued for about 3 hours while maintaining the temperature between 7.0 and 7.5. Next, at the same temperature, salting out with 20% sodium chloride based on the weight of the reaction solution was carried out, and the precipitated crystals were separated.
After drying, about 30 parts of the compound (6) was obtained. (Maximum absorption wavelength: 415, 520 nm (in 20% pyridine aqueous solution...the same applies hereinafter)) Example 2

[Chemical formula] 4.8 parts of nicotinic acid was added to 350 parts of a reaction solution containing 30 parts of the compound represented by formula (6) obtained in the same manner as in Example 1.
A solution completely dissolved in 25 parts of liquid caustic soda while adjusting the pH value to 6 to 7 was added, heated to 90 to 95°C while maintaining the pH value at 5.5 to 6.5, and reacted at the same temperature for 7 hours. Salting out was carried out at the same temperature as in Example 1, and the precipitated crystals were separated and dried to obtain 35 parts of the compound of formula (7). (Maximum absorption wavelength: 415, 520 nm) Example 3 According to the method described in Example 1, the following (8) is shown.

A compound represented by the following formula was obtained, and then 40 parts of the compound of formula (8) was dissolved in 400 parts, and 3.4 parts of nicotinic acid (0.7 times the theoretical amount) was added to this solution to adjust the pH value to 6.0.
This reaction solution was heated to 90℃, and while maintaining the pH between 5.7 and 6.3, the reaction was carried out at the same temperature for 8 hours.
Salting out with sodium chloride corresponding to % weight. The precipitated crystals were separated and dried to obtain 55 parts of brown powder. The obtained compound was analyzed by high performance liquid chromatography and the following results were obtained. (a) Compound represented by formula (8) 22% (b) One of the two chlorines in the compound represented by formula (8)
pieces

Replaced with [formula] 42% (c) Similarly, two chlorine

Substituted with [Formula] 27% (d) Structure unknown component 9% Examples 4 to 15 The chromium of the present invention represented by the following formula (9) was prepared in the same manner as described in Examples 1 and 2. Table 1 shows the maximum absorption wavelength (nm) of the synthesized compound and the hue when dyed on cotton.

[ka]

【table】

【table】

[Table] Example 17 2 parts of the target compound obtained in Example 2, 80 parts of Glauber's salt
1 part, 2 parts of Na ₂ HPO _{4.12H 20} and 0.5 part of KH ₂ PO ₄ , 1 part of sodium metanitrobenzenesulfonate and water
The dye bath PH at this time when a dye bath consisting of 934 parts was prepared
The value was 7. Add 50 parts of refined and bleached unsilced cotton stockinette to this dyebath, and add 30 parts while stirring.
The temperature was raised to 130°C in minutes, and staining was carried out at the same temperature for 30 minutes. The PH value after staining was 7, the same as before the start of staining. Next, it was washed with water and soaped at 100° C. for 10 minutes using 1000 parts of an aqueous solution containing 2 parts of an anionic surfactant, and then washed with water and dried to obtain a brown dyed product. This dyed product had excellent color yield. Example 18 1 part of the target compound obtained in Example 2 and the following composition: Kayacelon Orange E-2GL 0.285 parts Kayacelon Red E-GL 0.77 parts Kayacelon Blue E-BG 0.087 parts (all manufactured by Nippon Kayaku, disperse dyes) Contains disperse dye (brown), 80 parts of Glauber's salt, 2 parts of hommarine condensate of naphthalene sulfonic acid,
With a buffer consisting of Na ₂ HPO ₄ 12H ₂₀ and KH ₂ PO ₄
Polyester fiber/cotton (50/50) blended fabric (T/C blend) in a total dye bath of 1000 parts adjusted to PH7.0
50 parts were added, heated to 130°C over 20 minutes, and dyed at the same temperature for 60 minutes. After washing with water, 20% at 100℃ in 1000 parts of water containing 2 parts of anionic surfactant and 2 parts of soda ash.
After soaping for minutes, washing with water and drying, a dyed product with good color yield and uniformly brown dyeing on both the polyester fiber side and the cotton side was obtained. Example 19 2 parts of the target compound obtained in Example 1, anhydrous sodium sulfate
Prepare a dye bath using 60 parts and 918 parts of water.
Add 50 parts of unsilced cotton stockinette and heat at 80℃.
After treatment for 30 minutes, 20 parts of sodium carbonate were added and dyeing was continued for 60 minutes at the same temperature. Next, wash with water and prepare an aqueous solution containing 2 parts of anionic surfactant.
Soaping was carried out using 1,000 parts at 100° C. for 10 minutes, followed by washing with water and drying to obtain a brown dyed product. Comparative Test The color yield and aggregation properties of the compound of the present invention and the dye described in JP-A-60-76565 were compared, and the results shown below were obtained.

[Table] The above results were obtained by dyeing under the following dyeing conditions and evaluating the cohesiveness from the presence or absence of dye precipitation when anhydrous sodium sulfate was added to the dye bath. The color yield was evaluated by measuring the dyeing density. Conditions Γ dyed material: unsilced cotton knitted Γ dyeing density: 1, 2, 4, 8% (owf) Γ dyeing conditions: bath ratio 1:20 dyeing aid anhydrous mirabilite 80 parts Na ₂ HPO ₄・12H ₂ O 2 Part KH ₂ PO ₄ 0.5 part Sodium metanitrobenzenesulfonate 1 part Add 50 parts of the material to be dyed to the above dye bath, and in 30 minutes
℃, dyed at the same temperature for 30 minutes, washed with water and hot water, and then dyed with anionic surfactant 2.
Using 1000 parts of an aqueous solution containing 1,000 parts, the sample was soaped at 100°C for 10 minutes, washed with water, and dried. Note that the Qt value in FIG. 1 is measured by the following formula and is used as a measure of dyeing concentration. Qt=QX+QY+QZ QX=∫Pλλ(K/S)λdλ QY=∫Pλλ(K/S)λdλ QZ=∫Pλλ(K/S)λdλ (K/S)λ=(1−pλ) ² /2pλ λ= Wavelength λ, λ, λ: CIE spectrum tristimulus value Pλ: Reflectance (K/S) λ: K/S value Effects of the invention The water-soluble azo compound obtained by the present invention has color yield, build-up property, and aggregation. It has good properties and solubility, and extremely excellent results were obtained for dyeing T/C mixtures in one bath and one step when used in common reactive dye dyeing methods and in combination with disperse dyes and the like.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between staining concentration (owf) and Qt value (dying concentration). In other words, the horizontal axis shows the value obtained by dividing the specified amount of dye used by the amount of cotton used (%, ow
f) The vertical axis represents the Qt value.

Claims (1)

[Claims] 1 Formula (1) in the form of a free acid [Formula (1), X ₁ and X ₂ are each independently H, CH ₃ ,
OCH ₃ , NHCOCH ₃ or NHCONH ₂ , Y ₁ , Y ₂
each independently represents [Formula] [Formula] or Cl, n represents 1 or 2, and K ⁺ represents a cationic group] A chromium complex compound represented by the following. 2 In the form of a free acid, the formula (1) [Formula (1), X ₁ and X ₂ are each independently H, CH ₃ ,
OCH ₃ , NHCOCH ₃ or NHCONH ₂ , Y ₁ , Y ₂
each independently represents [Formula] [Formula] or Cl, n represents 1 or 2, and K ⁺ represents a cationic group] A method for dyeing cellulose fibers characterized by using a chromium complex compound represented by the following: .